N-(2-benzothiazoyl)-1, 4, 5, 8 diamino dihydroxy anthraquinones, mixtures and synthesis thereof



United States Patent 3,199,941 N (2 BENZOTHIAZOYL) 1,4,5,8 DIAMENODill-EY- DROXY ANTHRAQUINUNES, MIXTURES AND SYNTHESIS THEREOF AndrAlbert Paul Simonnet, Creil, and Louis Antoine Cabut, Nogent-sur-Oise,France, assignors, by mesne assignments, to Etablissements Kuhlrnann,Paris, France, a corporation of France N0 Drawing. Filed July 10, 1962,Ser. No. 208,934 Claims priority, application grantee, Aug. 21, 1961,

7 Claims. Yer. 8-25) The present invention relates to new dyestulfs forsynthetic fibres, especially fibres based on polyesters.

According to the present invention therefore, dyestufis are providedwhich are represented by the general formula:

in which one Y represents a hydrogen atom and the other aZ-benzothiazolyl residue, possibly substituted in the 6 position by anitro or amino group. The invention includes mixtures of these dyestuffswith one another.

The invention also includes a process for the preparation of dyestufisof Formula I Which com-prises reacting a compound of the generalformula:

in which X represents a hydrogen atom or a nitro or amino group, with adiamino-dihydroxy-anthraquinone of the general formula:

(III) "ice be obtained by nitration of anthrarufin, ehrysazin ormixtures of these substances and subsequent reduction of the mixtures ofnitro derivatives obtained. The nitration may be effected for example bymeans of fuming nitric acid or a mixture of sulphuric and nitric acidsaccording to known methods.

The dyestuffs according to the invention are suitable for thecolouration of synthetic fibres, especially fibres based on polyesters.By fibres based on polyesters are meant the fibres obtained bypolycondensa-tion of terephthalic acid with ethylene glycol. Such fibresare known on the market for example under thenames of Tel-gal, Dacron,and Terylene. The new dyestuffs have a very good afiin'ity for thesefibres, which they colour in full-bodied shades; the latter are alsocharacterised by their excellent fastness to light and sublimation.

The following examples, in which the parts given are parts by weight,illustrate the invention without limiting it.

Example 1 11 parts of a mixture containing 5.5 parts of 1,5-di-.aminmanthrarufin and 5.5 parts of 1,8-d'iam-ino-chrysazin are graduallydissolved in parts of melted phenol. This mixture is then heated to C.As soon as this temperature is reached, 8.2 parts of 2-chlorobenzothiazole are added and the reaction is continued for 24 hoursduring which the temperature is maintained at 150 C. to C. After coolingto 70 C., 1000 parts of ethyl alcohol are add-ed and the mixture isfiltered. The precipitate is then washed with alcohol until the washingsare colourless, and is drained and dried. 13.7 parts of .a blue powderare thus obtained, the elementary analysis of which is established asfollows.

Calculated for C H N O S: C, 62.3%; H, 3.22%; N, 10.4%; S, 7.92%. Found:C, 61.61%; H, 3.45%; N, 10.21%; S, 8.21%.

The .dyestuff, previously dispersed, dyes fibres based on polyesters abrightblue which is very fast to light-and to sublimation.

Example 2 If in Example 1 the 2-chloro-benz-o=thiazole is replaced by10.3 parts of 2-chlor-o 6-nitro benzothiazole, the dyestuff obtaineddyes fibres based on polyesters a blue slightly greenish shade which isvery fiast to light and to sublimation.

Example 3' On replacing the 2-chloro-benzotbiazole in Example 1 by 8.9parts of 2-chloro-6-amino-benzothiazole, there are obtained 15.85 par-tsof a dyest-ufi which dyes fibres based on polyesters a reddish blueshade endowed with good rastness.

Example 4 Example 5 10 parts of anthrarufin are introduced in smallportions and with stirring into 40 parts of 48 B. nitric acid at atemperature of 0 C. to 3 C. Stirring is continued for 4 hours while thetemperature is maintained at about C., thenthe mixture is introducedinto 500 parts of ice water. The nitro derivatives which precipitate arefiltered 01f, washed until neutral and dried. 12.1 parts of anorange-yellow powder are obtained; this is introduced into 242 parts ofa 5% solution of sodium sulphide and reduced for 1 hour at 90 C. to 95C. After cooling, the diamino derivatives are precipitated by theaddition of ammonium chloride, filtered off, washed and dried. 9.4 partsof a mixture consisting essentially of 4,8-diamino-, 2,8-diamino-, and2,6-diamino-anthrarufins are obtained; elementary analysis gave thefollowing results. [Calculated for C H O N N, 10.36%. Found: N, 10.41%.1

6 parts of this mixture of diamino-anthrarufins are dissolved graduallyin 40 parts of melted phenol. Thissolution is then heated to 120 C. Whenthis temperature is reached, 4.1'parts of 2-chloro-benzotl1iazole areintroduced and the reaction is continued for 22 hours while thetemperature is raised to about 150 C. to 160 C. After cooling to 70 C.,500 parts of ethyl alcohol are added and the precipitate is filtered01f, then washed with boiling alcohol until the washings are colourless,drained and dried. 8.2 parts of a brown powder are thus obtained, theelementary analysis of which gave the following results. i a aCalculated fOI C21II13OV4N3SI N, Found: N, 10.20%; S, 8.50%. p

This powder, previously dispersed, dyes fibres based on polyesters afull-bodied violet shade which is very fast to light and to sublimation.

Example 6 19.2 parts of anthrarufin are dissolved in 180 parts of 5of'boil-ing water. The diamino-anthrarufins are precipitated in thefiltrates by the addition of sodium bicarbonate, filtered 01f, washeduntil neutral and dried. of a brown powder are thus obtained, thegreater part of which consists of 2,6-diaminoand 2,8-diaminoanthra- 5.4parts of this mixture are treated with 3.75 parts ofZ-chloro-benzothiazole in 40 parts of phenol, in accordance with theprocess described in Example 5. 6.6 parts of a brown powder are obtainedwhich, after dispersion, 'dyes fibresbased on polyesters a red-violetshade possessing excellent fastness' to light and sublimation. j

Example 7 I Example 8 If 19.2 parts of chrysazin are used in Example 6instead of 19.2 parts of anthrarufin, 4.7 parts of a mixture consistingprincipally of 2,7-diamino-' and 2,5diamino-chrysazin are obtained. Whentreated under the same conditions it gives 6.4 parts of a mixture ofdyestuffs which dyes fibres based on polyesters a violet blue shadewhich is very fast to light and sublimation.

10.2 parts Example 9 The procedure is as in Example 5 but with chrysazininstead of anthrarufin. A mixture of dyestuffs is obtained which dyesfibres based on polyesters a reddish blue shade having very goodfastness to sublimation.

We claim: 1. Dyestuifs mixtures of they general formula:

. on o 1 ill Y b p (I) in which one Y represents a hydrogen atom and theother Y represents a member selected from the group consisting of the2-benzothiazoly1 residue, the 2-benzothiaz0lyl residue substituted inthe 6 position by 2. nitro group and the Z-benzothiazolyl residuesubstituted in the 6 position by an. amino group.

2. Mixtures of dyestuffs of the in claim 1.

3. Mixtures of dyestufis consisting ofN-(Z-monobenzothiazolyl)-l,5-diamino-anthrarufin V andN-(Z-monobenzothiazolyl)-1,8-diamino-chrysazin.

4. The mixture of dyestuffs consisting of N-(Z-monobenzothiazolyl-4,8-diamino-anthrarufin, N-(2-monobenzothiazolyl)-2,8-diamino-anthrarufin, andN-(Z-monobenzothiazolyl)-2,6 diamino-anthrarufin.

5. Process for the preparation of dyestuifs which comprises reacting acompound of the general formula:

N in which X represents a member selected from the group consisting ofthe hydrogen atom and the nitro and amino groups with at least onediamino dihydroxy anthraquinone of the general formula:

general formula given 1; (III) 6. Process as claimed in claim 5 in whichthe reaction is effected in an organicsolvent.

7. Process as claimed in claim 5 in which the reaction is efiected inphenol at a temperature between C. and 200 C.

References Cited by theExarniner UNITED STATES PATENTS 2,060,186 11/36Felix 8-25 2,099,673 11/37 Beard 260-303 2,342,191 2/44 Grossmann 8-252,899,438 8/59 Jenny 260-303 2,982,773 5/61 Grossman 260--377 OTHERREFERENCES Review of Textile Progress, 1961, pp. 227-228, pub. 1962 by,Butterworth & Co.-, Washington, DC.

NORMAN G. TORCHIN, Primary Examinen. ABRAHAM H. WINKELSTEIN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,199,941 August 10, 1965 Andre Albert Paul Simonnet et aln It is herebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

In the heading to the printed specification, line 11, after "871,188"insert --;Oct, 25, 1961, 876,975 --u Signed and sealed this 19th day ofApril 1966.

(SEAL) Attest: 1 ERNEST W. SWIDER EDWARD J. BRENNER Attesting OfficerCommissioner of Patents

3. MIXTURES OF DYESTUFFS CONSISTING OFN-(2-MONOBENZOTHIAZOLYL)-1,5-DIAMINO-ANTHRARUFIN ANDN-(2-MONOBENZOTHIAZOLYL)-1,8-DIAMINO-CHRYSAZIN.